EP2620441B1 - Polysiloxane modifié à structure polyédrique, composition à base de polysiloxane à structure polyédrique, produit durci, et dispositif semi-conducteur optique - Google Patents
Polysiloxane modifié à structure polyédrique, composition à base de polysiloxane à structure polyédrique, produit durci, et dispositif semi-conducteur optique Download PDFInfo
- Publication number
- EP2620441B1 EP2620441B1 EP11826768.1A EP11826768A EP2620441B1 EP 2620441 B1 EP2620441 B1 EP 2620441B1 EP 11826768 A EP11826768 A EP 11826768A EP 2620441 B1 EP2620441 B1 EP 2620441B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyhedral polysiloxane
- group
- compound
- alkenyl
- aryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 polysiloxane Polymers 0.000 title claims description 344
- 229920001296 polysiloxane Polymers 0.000 title claims description 210
- 239000000203 mixture Substances 0.000 title claims description 120
- 230000003287 optical effect Effects 0.000 title claims description 33
- 239000004065 semiconductor Substances 0.000 title claims description 18
- 125000003342 alkenyl group Chemical group 0.000 claims description 110
- 150000001875 compounds Chemical class 0.000 claims description 74
- 125000003118 aryl group Chemical group 0.000 claims description 46
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 150000002894 organic compounds Chemical class 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 229910020487 SiO3/2 Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 150000003377 silicon compounds Chemical class 0.000 claims description 12
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 11
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
- UCBVELLBUAKUNE-UHFFFAOYSA-N 1,3-bis(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)NC(=O)N(CC=C)C1=O UCBVELLBUAKUNE-UHFFFAOYSA-N 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 96
- 239000000047 product Substances 0.000 description 50
- 239000000463 material Substances 0.000 description 47
- 239000000243 solution Substances 0.000 description 42
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 33
- 238000012360 testing method Methods 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 30
- 239000010408 film Substances 0.000 description 27
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 239000007983 Tris buffer Substances 0.000 description 17
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- POPVULPQMGGUMJ-UHFFFAOYSA-N octasilsesquioxane cage Chemical compound O1[SiH](O[SiH](O2)O[SiH](O3)O4)O[SiH]4O[SiH]4O[SiH]1O[SiH]2O[SiH]3O4 POPVULPQMGGUMJ-UHFFFAOYSA-N 0.000 description 15
- 229910052697 platinum Inorganic materials 0.000 description 15
- 239000011521 glass Substances 0.000 description 14
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- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 10
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 10
- ODEXJPXBFISZCB-UHFFFAOYSA-N ethenyl-methyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=C)(C)C1=CC=CC=C1 ODEXJPXBFISZCB-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
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- 238000002156 mixing Methods 0.000 description 8
- OOGRAMOPTBMVKO-UHFFFAOYSA-N bis[[ethenyl(dimethyl)silyl]oxy]-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](O[Si](C)(C)C=C)(O[Si](C)(C)C=C)C1=CC=CC=C1 OOGRAMOPTBMVKO-UHFFFAOYSA-N 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 238000002161 passivation Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
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- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
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- 238000009833 condensation Methods 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
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- 230000009257 reactivity Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- OVOIHGSHJGMSMZ-UHFFFAOYSA-N ethenyl(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=C)C1=CC=CC=C1 OVOIHGSHJGMSMZ-UHFFFAOYSA-N 0.000 description 3
- QDEZCOQKJSRQNN-UHFFFAOYSA-N ethenyl-dimethyl-phenylsilane Chemical compound C=C[Si](C)(C)C1=CC=CC=C1 QDEZCOQKJSRQNN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
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- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 3
- 229920001843 polymethylhydrosiloxane Chemical group 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
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- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
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- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
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- 0 *N(C(N(*)C(N1O)=O)=O)C1=O Chemical compound *N(C(N(*)C(N1O)=O)=O)C1=O 0.000 description 1
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- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 1
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- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- ASGKDLGXPOIMTM-UHFFFAOYSA-N diethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](C)(OCC)OCC)CCC2OC21 ASGKDLGXPOIMTM-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- YVLWMUQPCXXHEZ-UHFFFAOYSA-N diethyl(2-phenylethenyl)silane Chemical compound CC[SiH](CC)C=CC1=CC=CC=C1 YVLWMUQPCXXHEZ-UHFFFAOYSA-N 0.000 description 1
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 1
- SLQTWNAJXFHMHM-UHFFFAOYSA-N dimethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](C)(OC)OC)CCC2OC21 SLQTWNAJXFHMHM-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- VYKLWEGAUSVCDK-UHFFFAOYSA-N dimethyl-phenyl-prop-2-enylsilane Chemical compound C=CC[Si](C)(C)C1=CC=CC=C1 VYKLWEGAUSVCDK-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- HBWGDHDXAMFADB-UHFFFAOYSA-N ethenyl(triethyl)silane Chemical compound CC[Si](CC)(CC)C=C HBWGDHDXAMFADB-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- YYQBYVVVXNLVGV-UHFFFAOYSA-N methyl-diphenyl-prop-2-enylsilane Chemical compound C=1C=CC=CC=1[Si](CC=C)(C)C1=CC=CC=C1 YYQBYVVVXNLVGV-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000001393 microlithography Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- LDIPAUVCWRHLAM-UHFFFAOYSA-N n',n'-dibutylbutane-1,4-diamine Chemical compound CCCCN(CCCC)CCCCN LDIPAUVCWRHLAM-UHFFFAOYSA-N 0.000 description 1
- PWNDYKKNXVKQJO-UHFFFAOYSA-N n',n'-dibutylethane-1,2-diamine Chemical compound CCCCN(CCN)CCCC PWNDYKKNXVKQJO-UHFFFAOYSA-N 0.000 description 1
- KYCGURZGBKFEQB-UHFFFAOYSA-N n',n'-dibutylpropane-1,3-diamine Chemical compound CCCCN(CCCC)CCCN KYCGURZGBKFEQB-UHFFFAOYSA-N 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- PKELYQZIUROQSI-UHFFFAOYSA-N phosphane;platinum Chemical class P.[Pt] PKELYQZIUROQSI-UHFFFAOYSA-N 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- SYKXNRFLNZUGAJ-UHFFFAOYSA-R platinum;triphenylphosphanium Chemical compound [Pt].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 SYKXNRFLNZUGAJ-UHFFFAOYSA-R 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 description 1
- WDUXKFKVDQRWJN-UHFFFAOYSA-N triethoxysilylmethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C=C WDUXKFKVDQRWJN-UHFFFAOYSA-N 0.000 description 1
- SVGQCVJXVAMCPM-UHFFFAOYSA-N triethyl(prop-2-enyl)silane Chemical compound CC[Si](CC)(CC)CC=C SVGQCVJXVAMCPM-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
- 238000006227 trimethylsilylation reaction Methods 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- DXJZZRSMGLGFPW-UHFFFAOYSA-N triphenyl(prop-2-enyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(CC=C)C1=CC=CC=C1 DXJZZRSMGLGFPW-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/008—Additives improving gas barrier properties
Definitions
- the present invention relates to a modified polyhedral polysiloxane, a polyhedral polysiloxane composition, a cured product, and an optical semiconductor device.
- compositions are used in various industries because of their excellence in heat resistance, cold resistance, weather resistance, light resistance, chemical stability, electrical characteristics, flame retardancy, water resistance, transparency, colorability, anti-adhesive properties, and anti-corrosive properties.
- compositions containing polyhedral polysiloxanes are known to have even better properties due to the unique chemical structures of the polyhedral polysiloxanes, such as greater heat resistance, greater light resistance, greater chemical stability, and lower dielectric properties.
- Patent Literature 1 discloses a polyhedral polysiloxane composition containing a polyhedral polysiloxane resin having at least two oxetanyl groups, an aliphatic hydrocarbon having at least one epoxy group, and a cationic polymerization initiator. This material has a high refractive index and high light extraction efficiency.
- the polysiloxane composition of Patent Literature 1 has problems attributed to the oxetanyl and epoxy groups, such as low heat resistance and low light resistance.
- Patent Literature 2 uses an epoxy group-containing polyorganopolysiloxane with the limited glass transition temperature to improve the problems in heat resistance and light resistance. This material is also thought to be more resistant to cracking even after a thermal shock test.
- polysiloxane compositions generally have the problem of low gas-barrier properties.
- these compositions when used as encapsulants for optical semiconductor devices, may allow sulfides to turn reflectors black.
- An exemplary strategy to deal with this problem is to coat metal members with an acrylic resin having high gas-barrier properties in advance before encapsulating them with a silicone resin as disclosed in Patent Literature 3.
- the silicone resin used in this technique itself has low gas-barrier properties, and additionally, this technique is problematic in terms of productivity because it requires extra steps such as encapsulation with a silicone resin separately after the coating treatment with an acrylic resin.
- encapsulants containing a yellow phosphor are used for blue light emitting devices in order to produce white light; or encapsulants containing green and red phosphors are used for blue light emitting devices in order to improve color rendition.
- encapsulants containing green and red phosphors are used for blue light emitting devices in order to improve color rendition.
- the phosphors may settle during the handling of the encapsulants to cause the problem of variation in emission color.
- Patent Literature 4 discloses a composition containing a modified polyhedral polysiloxane which has excellent moldability/processability, transparency, heat and light resistance, and adhesion. However, this material still leaves room for improvement in terms of the viscosity (handleability) of the composition and gas-barrier properties.
- EP 2 151 443 A1 discloses a modified product of polyhedral polysiloxane which is obtainable by modifying a polyhedral polysiloxane compound (a) with a compound (b), and a composition containing the modified product.
- the polyhedral polysiloxane compound (a) has an alkenyl group and/or a hydrosilyl group
- the compound (b) has a hydrosilyl group and/or an alkenyl group each capable of hydrosilylation with the component (a).
- the present invention provides a polyhedral polysiloxane composition that has high heat resistance and high light resistance, is excellent in gas-barrier properties and thermal shock resistance, and exhibits good handleability when used to encapsulate an optical semiconductor device or the like; a modified polyhedral polysiloxane for such a composition; and a cured product and an optical semiconductor device including such a composition.
- the present inventors have made intensive studies to solve the above problems, and finally completed a modified polyhedral polysiloxane, a polyhedral polysiloxane composition, a cured product, and an optical semiconductor device which have features described below.
- the present invention provides a polyhedral polysiloxane composition that has high heat resistance and high light resistance, is excellent in gas-barrier properties and thermal shock resistance, and exhibits good handleability when used to encapsulate an optical semiconductor device.
- the present invention also provides a modified polyhedral polysiloxane that is suitable as a component of a polyhedral polysiloxane composition having the above properties.
- the present invention further provides a cured product that has high heat resistance and high light resistance, and is excellent in gas-barrier properties and thermal shock resistance, and an optical semiconductor device including an encapsulant having these properties.
- the modified polyhedral polysiloxane of the present invention is a modified polyhedral polysiloxane obtained by hydrosilylation of an alkenyl group-containing polyhedral polysiloxane compound (a) and a hydrosilyl group-containing compound (b), and has a structure derived from an organic silicon compound (a') having one alkenyl group per molecule.
- the alkenyl group-containing polyhedral polysiloxane compound (a) used in the present invention is not particularly limited, provided that it is a polyhedral polysiloxane containing an alkenyl group in its molecule.
- Preferred specific examples include alkenyl group-containing polyhedral polysiloxane compounds that contain siloxane units represented by the formula: [R 6 SiO 3/2 ] x [R 7 SiO 3/2 ] y wherein x+y is an integer of 6 to 24, provided that x is an integer of 1 or larger and y is an integer of 0 or 1 or larger; R 6 is an alkenyl group or a group containing an alkenyl group; and R 7 is any organic group or a group bonded to another polyhedral polysiloxane.
- alkenyl group-containing polyhedral polysiloxane compounds that contain siloxane units represented by the formula: [AR 1 2 SiO-SiO 3/2 ] a [R 2 3 SiO-SiO 3/2 ] b wherein a+b is an integer of 6 to 24, provided that a is an integer of 1 or larger and b is an integer of 0 or 1 or larger;
- A is alkenyl;
- R 1 is alkyl or aryl; and R 2 is hydrogen, alkyl, aryl or a group bonded to another polyhedral polysiloxane.
- alkenyl groups examples include vinyl, allyl, butenyl, and hexenyl. In terms of the heat resistance and light resistance, vinyl is preferred.
- R 1 is alkyl or aryl.
- alkyl groups include methyl, ethyl, propyl, butyl, cyclohexyl, and cyclopentyl
- aryl groups include phenyl and tolyl.
- R 1 is preferably methyl in terms of the heat resistance and light resistance.
- R 2 is hydrogen, alkyl, aryl, or a group bonded to another polyhedral polysiloxane.
- alkyl groups include methyl, ethyl, propyl, butyl, cyclohexyl, and cyclopentyl
- aryl groups include phenyl and tolyl.
- R 2 is preferably methyl in terms of the heat resistance and light resistance.
- a is not particularly limited, provided that it is an integer of 1 or larger.
- a is preferably 2 or larger, and more preferably 3 or larger.
- the symbol b is not particularly limited, provided that it is an integer of 0 or 1 or larger.
- the component (a) can be synthesized by any known methods without particular limitation.
- An exemplary synthesis method is hydrolysis-condensation of a silane compound represented by the formula: R 8 SiX a 3 wherein R 8 represents R 6 or R 7 described above, and X a represents halogen or a hydrolyzable functional group such as an alkoxy group.
- Also known is a method for synthesizing a polyhedral polysiloxane which involves synthesizing a trisilanol compound that has three silanol groups per molecule by hydrolysis-condensation of a compound of R 8 SiX a 3 , and then reacting the trisilanol compound with a trifunctional silane compound that is the same as or different from the former to form a closed ring.
- Still another example is hydrolysis-condensation of a tetraalkoxysilane such as tetraethoxysilane in the presence of a base such as a quaternary ammonium hydroxide.
- a tetraalkoxysilane such as tetraethoxysilane
- a base such as a quaternary ammonium hydroxide.
- the hydrolysis-condensation of a tetraalkoxysilane produces a polyhedral silicate
- the resulting silicate is further reacted with a silylating agent such as an alkenyl group-containing silyl chloride to provide a polyhedral polysiloxane in which Si atoms forming a polyhedral structure and an alkenyl group are bonded via siloxane bonds.
- the tetraalkoxysilane may be replaced by silica or a material containing silica such as rice husk to produce
- the organic silicon compound (a') having one alkenyl group per molecule in the present invention reacts with the hydrosilyl group of the hydrosilyl group-containing compound (b).
- the use of the component (a') reduces the elastic modulus of cured products to be obtained and improves the thermal shock resistance.
- compositions are used as encapsulants for LEDs, it is possible to inhibit phosphors from settling.
- alkenyl group examples include vinyl, allyl, butenyl, and hexenyl. In terms of the heat resistance and light resistance, vinyl is preferred.
- the component (a') in the present invention is not particularly limited as long as it is an organic silicon compound having one alkenyl group per molecule and, in terms of the gas-barrier properties and refractive index, has at least one aryl group per molecule. More preferably, in terms of the heat resistance and light resistance, the aryl group is directly bonded to a silicon atom.
- the component (a') in the present invention is preferably a silane or a polysiloxane in terms of the heat resistance and light resistance.
- silanes having one alkenyl group per molecule as the component (a') include trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, triphenylvinylsilane, triethylvinylsilane, diethylphenylvinylsilane, ethyldiphenylvinylsilane, allyltrimethylsilane, allyldimethylphenylsilane, allylmethyldiphenylsilane, allyltriphenylsilane, allyltriethylsilane, allyldiethylphenylsilane, and allylethyldiphenylsilane.
- preferred examples include trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, and triphenylvinylsilane; and in terms of the gas-barrier properties and refractive index, preferred examples include dimethylphenylvinylsilane, methyldiphenylvinylsilane, and triphenylvinylsilane.
- component (a') is a polysiloxane
- linear polysiloxanes having one alkenyl group as the component (a') include polydimethylsiloxanes whose ends are terminated with one dimethylvinylsilyl group and one trimethylsilyl group, respectively, polymethylphenylsiloxanes whose ends are terminated with one dimethylvinylsilyl group and one trimethylsilyl group, respectively, polydiphenylsiloxanes whose ends are terminated with one dimethyl vinyl silyl group and one trimethylsilyl group, respectively, copolymers containing dimethylsiloxane units and methylphenylsiloxane units of which ends are terminated with one dimethylvinylsilyl group and one trimethylsilyl group, respectively, copolymers containing dimethylsiloxane units and diphenylsiloxane units of which ends are terminated with one dimethylvinylsilyl group and one trimethylsilyl group, respectively, copolymers containing dimethylsiloxane units
- polysiloxanes having one alkenyl group at a molecular end include polysiloxanes whose ends are terminated with one dimethylvinylsilyl group and one trimethylsilyl group, respectively, as mentioned above, and polysiloxanes containing one dimethylvinylsiloxane unit and at least one siloxane unit selected from the group consisting of SiO 2 unit, SiO 3/2 unit, SiO unit, and SiO 1/2 unit.
- cyclic siloxanes having one alkenyl group as the component (a') include 1-vinyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1-vinyl-3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-vinyl-3,5-diphenyl-1,3,5,7,7-pentamethylcyclotetrasiloxane, and 1-vinyl-3,5,7-triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane.
- any of these organic silicon compounds having one alkenyl group per molecule as the component (a') may be used alone, or two or more of these may be used in combination.
- the hydrosilyl group-containing compound (b) used in the present invention is not particularly limited, provided that it has at least one hydrosilyl group per molecule.
- the compound (b) is preferably a hydrosilyl group-containing siloxane compound, and more preferably a hydrosilyl group-containing cyclic siloxane or a hydrosilyl group-containing linear polysiloxane.
- it is preferably a cyclic siloxane in terms of the heat resistance, light resistance, blue laser resistance, and gas-barrier properties.
- hydrosilyl group-containing linear polysiloxane examples include copolymers containing dimethylsiloxane units, methylhydrogensiloxane units, and terminal trimethylsiloxy units; copolymers containing diphenylsiloxane units, methylhydrogensiloxane units, and terminal trimethylsiloxy units; copolymers containing methylphenylsiloxane units, methylhydrogensiloxane units, and terminal trimethylsiloxy units; dimethylhydrogensilyl group-terminated polydimethylsiloxanes; dimethylhydrogensilyl group-terminated polydiphenylsiloxanes; and dimethylhydrogensilyl group-terminated polymethylphenylsiloxanes.
- dimethylhydrogensilyl group-terminated polysiloxanes in terms of the reactivity in modification, the heat resistance and light resistance of cured products to be obtained, and the like, dimethylhydrogensilyl group-terminated polysiloxanes, more preferably, dimethylhydrogensilyl group-terminated polydimethylsiloxanes can be suitably used as the hydrosilyl group-containing linear polysiloxane.
- Preferred specific examples include tetramethyldisiloxane and hexamethyltrisiloxane.
- hydrosilyl group-containing cyclic siloxane examples include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, and 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane.
- 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane is suitable as the cyclic siloxane in terms of the industrial availability and reactivity, the heat resistance, light resistance, and strength of cured products to be obtained, and the like.
- hydrosilyl group-containing compounds as the component (b) may be used alone, or two or more of these may be used in combination.
- the modified polyhedral polysiloxane of the present invention can be obtained by hydrosilylation of an alkenyl group-containing polyhedral polysiloxane compound (a) and an organic silicon compound (a') having one alkenyl group per molecule with a hydrosilyl group-containing compound (b) in the presence of a later-described hydrosilylation catalyst.
- the component (a) and the component (b) may be reacted first, followed by reaction with the component (a'), or the component (a') and the component (b) may be reacted first, followed by reaction with the component (a).
- the component (a) and the component (a') may be simultaneously reacted with the component (b).
- volatile unreacted components may be evaporated, for example, under reduced pressure and heating, to obtain the target product or an intermediate for a subsequent step.
- the component (a) and the component (b) be reacted, followed by evaporation of the unreacted component (b) and then reaction with the component (a').
- Part of alkenyl groups from the component (a) used in the reaction may be left in the modified polyhedral polysiloxane thus obtained.
- the amount of the component (b) is preferably determined so that the number of hydrosilyl groups is 2.5 to 20 per alkenyl group of the component (a). If the amount is small, then the cross-linking reaction accelerates gelation, possibly resulting in a modified polyhedral polysiloxane with poor handleability. If the amount is large, the physical properties of the cured products may be adversely affected.
- the amount of the component (a') is preferably determined so that the number of alkenyl groups is 0.01 to 0.36 per hydrosilyl group of the component (b). If the amount is small, the effect of improving the thermal shock resistance of cured products to be obtained may be small, whereas if the amount is large, cured products that have been insufficiently cured may be obtained.
- the amount of the hydrosilylation catalyst used in synthesis of the modified polyhedral polysiloxane is not particularly limited, and is preferably 10 -1 to 10 -10 mol, and more preferably 10 -4 to 10 -8 mol, per mol of alkenyl groups of the components (a) and (a') used in the reaction. Since some hydrosilylation catalysts absorb light with short wavelengths, the use of a large amount of hydrosilylation catalyst may cause coloring. Additionally, then cured products to be obtained may have reduced light resistance and may be foamed. The use of a small amount of hydrosilylation catalyst may not allow the reaction to proceed, and thus the target product may not be provided.
- the reaction temperature of the hydrosilylation is about 30 to 400°C and is preferably 40 to 250°C, more preferably 45 to 140°C. At too low temperatures, the reaction may not proceed to a sufficient extent, whereas at too high temperatures, gelation may occur leading to poor handleability.
- the modified polyhedral polysiloxane of the present invention may be a polyhedral polysiloxane compound containing a siloxane unit represented by the formula: [XR 3 2 SiO-SiO 3/2 ] a [R 4 3 SiO-SiO 3/2 ] b wherein a+b is an integer of 6 to 24, provided that a is an integer of 1 or larger and b is an integer of 0 or 1 or larger; R 3 is alkyl or aryl; R 4 is alkenyl, hydrogen, alkyl, aryl, or a group bonded to another polyhedral polysiloxane; and X has a structure represented by the following formula (1) or (2), and in the case where multiple Xs are present, the structures of the formula (1) or (2) may be different from one another and the structures of the formulas (1) and (2) may coexist: wherein 1 is an integer of 2 or larger; m is an integer of 0 or larger; n is an integer of 2 or larger; Y
- R 5 is not particularly limited as long as it is a group containing a silicon compound.
- R 5 preferably has at least one aryl group per molecule. More preferably, in terms of the heat resistance and light resistance, the aryl group is directly bonded to a silicon atom.
- the above-described modified polyhedral polysiloxane of the present invention certainly has compatibility with various compounds, specifically with the later-described component (B) . Additionally, due to the presence of the hydrosilyl group in its molecule, it can react with various alkenyl group-containing compounds. More specifically, it can react with a polysiloxane (B1) or organic compound (B2) having at least two alkenyl groups per molecule mentioned later to give a cured product having excellent heat resistance, light resistance, blue laser resistance, and gas-barrier properties.
- the modified polyhedral polysiloxane of the present invention can be prepared in liquid form at 20°C.
- the modified polyhedral polysiloxane in liquid form is preferred because it is easy to handle.
- the modified polyhedral polysiloxane of the present invention preferably has at least three hydrosilyl groups on average per molecule.
- the polyhedral polysiloxane composition of the present invention is characterized by containing the above-described modified polyhedral polysiloxane of the present invention (hereinafter, also referred to as modified polyhedral polysiloxane (A)), and may further contain a compound (B) having at least two alkenyl groups per molecule.
- the composition of the present invention contains the compound (B)
- the composition is cured into a cured product as a result of hydrosilylation of the alkenyl group of the compound (B) with the hydrosilyl group of the modified polyhedral polysiloxane (A).
- the hydrosilylation is preferably performed in the presence of a hydrosilylation catalyst.
- hydrosilylation catalysts usable in this reaction are mentioned later.
- the amount of the compound (B) can be determined as desired, and the compound (B) is preferably added so that the number of hydrosilyl groups of the modified polyhedral polysiloxane (A) is 0.3 to 5, more preferably 0.5 to 3, per alkenyl group. If the ratio of alkenyl groups is too small, a poor appearance due to foaming or the like is likely to be caused. Also, if the ratio of alkenyl groups is too large, the physical properties after curing may be adversely affected.
- the compound (B) is preferably a polysiloxane (B1) having at least two alkenyl groups per molecule, a later-described organic compound (B2), or the like.
- the components (B1) and (B2) may be used in combination.
- the number of siloxane units in the polysiloxane (B1) having at least two alkenyl groups per molecule is not particularly limited, and is preferably not less than 2, and more preferably 2 to 10. If the number of siloxane units per molecule is small, then the polysiloxane tends to evaporate easily from the composition and desired physical properties may not be obtained after curing. Also, if the number of siloxane units is large, cured products with reduced gas-barrier properties may be obtained.
- the polysiloxane (B1) having at least two alkenyl groups per molecule preferably contains an aryl group.
- the aryl group of the aryl group-containing polysiloxane having at least two alkenyl groups per molecule is preferably bonded directly to an Si atom.
- the aryl group may be located either in a side chain or at an end of the molecule.
- the molecular structure of the aryl group-containing polysiloxane is not limited and may be, for example, a linear structure, a branched structure, a partially branched linear structure, or a cyclic structure.
- aryl group examples include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-propylphenyl, 3-propylphenyl, 4-propylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 2-butylphenyl, 3-butylphenyl, 4-butylphenyl, 3-isobutylphenyl, 4-isobutylphenyl, 3-t-butylphenyl, 4-t-butylphenyl, 3-pentylphenyl, 4-pentylphenyl, 3-hexylphenyl, 4-hexylphenyl, 3-cyclohexylphenyl, 4-cyclohexylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-di
- preferred examples of the polysiloxane (B1) having at least two alkenyl groups per molecule include linear polysiloxanes having at least two alkenyl groups, polysiloxanes having at least two alkenyl groups at molecular end(s), and cyclic siloxanes having at least two alkenyl groups.
- linear polysiloxanes having at least two alkenyl groups include copolymers containing dimethylsiloxane units, methylvinylsiloxane units, and terminal trimethylsiloxy units; copolymers containing diphenylsiloxane units, methylvinylsiloxane units, and terminal trimethylsiloxy units; copolymers containing methylphenylsiloxane units, methylvinylsiloxane units, and terminal trimethylsiloxy units; dimethylvinylsilyl group-terminated polydimethylsiloxanes; dimethylvinylsilyl group-terminated polydiphenylsiloxanes; and dimethylvinylsilyl group-terminated polymethylphenylsiloxanes.
- polysiloxanes having at least two alkenyl groups at molecular end(s) include dimethylvinylsilyl group-terminated polysiloxanes mentioned above; and polysiloxanes containing two or more dimethylvinylsiloxane units and at least one siloxane unit selected from the group consisting of SiO 2 unit, SiO 3/2 unit, and SiO unit.
- cyclic siloxane compounds having at least two alkenyl groups include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-vinyl-1-phenyl-3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,5-diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3,5,7-trivinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7-divinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-1,3,5
- any of these polysiloxanes (B1) having at least two alkenyl groups per molecule may be used alone, or two or more of these may be used in combination.
- the component (B2) in the present invention functions as a crosslinker for the component (A) to provide a cured product having heat resistance, light resistance, and gas-barrier properties.
- the organic compound (B2) in the present invention is not particularly limited as long as it is an organic compound represented by the formula (4) below and having at least two alkenyl groups per molecule.
- R 9 s each represent a monovalent C 1-50 organic group or hydrogen, and may be the same as or different from one another.
- the presence of at least two alkenyl groups in each molecule of the component (B2) in the present invention contributes to excellent properties (e.g. strength, gas-barrier properties, heat resistance, light resistance) of cured products to be obtained.
- the component (B2) preferably has a number average molecular weight of less than 900.
- the component (B2) is preferably an isocyanuric acid derivative represented by the above formula (4) and having at least two alkenyl groups per molecule in terms of, for example, the adhesion between a substrate and the composition cured thereon, and is more preferably triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, or diallyl monoglycidyl isocyanurate in terms of the balance of the heat resistance and light resistance. In particular, diallyl monomethyl isocyanurate is still more preferred in terms of the thermal shock resistance.
- the component (B2) may contain a functional group other than alkenyl groups in its structure.
- a functional group other than alkenyl groups in its structure.
- preferred are low polar functional groups such as linear aliphatic hydrocarbon groups (e.g. methyl, ethyl, propyl).
- linear aliphatic hydrocarbon groups e.g. methyl, ethyl, propyl.
- methyl is preferred in terms of the heat resistance and light resistance.
- a hydrosilylation catalyst is used in synthesis of the modified polyhedral polysiloxane (A) and in curing of the polyhedral polysiloxane composition containing the modified product (A).
- any of generally known hydrosilylation catalysts can be used without particular limitation.
- platinum-olefin complexes chloroplatinic acid, elemental platinum, and carriers (such as alumina, silica, and carbon black) which carry solid platinum; platinum-vinylsiloxane complexes such as Pt n (ViMe 2 SiOSiMe 2 Vi) n and Pt[(MeViSiO) 4 ] m ; platinum-phosphine complexes such as Pt(PPh 3 ) 4 and Pt(PBu 3 ) 4 ; platinum-phosphite complexes such as Pt[P(OPh) 3 ] 4 and Pt[P(OBu) 3 ] 4 in which Me represents methyl, Bu represents butyl, Vi represents vinyl, Ph represents phenyl, and n and m each represent an integer; and Pt(acac) 2 .
- platinum-vinylsiloxane complexes such as Pt n (ViMe 2 SiOSiMe 2 Vi) n and Pt[(
- Examples of the catalysts other than platinum compounds include RhCl (PPh 3 ) 3 , RhCl 3 , Rh/Al 2 O 3 , RuCl 3 , IrCl 3 , FeCl 3 , AlCl 3 , PdCl 2 ⁇ 2H 3 O, NiCl 2 , and TiCl 4 .
- the catalysts may be used alone, or two or more of them may be used in combination.
- preferred are chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, Pt(acac) 2 , and the like.
- a cure retardant is a component to improve the storage stability of the polyhedral polysiloxane composition of the present invention or to control the reactivity in hydrosilylation in the curing process.
- the cure retardant used may be any one generally known to be used for addition-curable compositions curable in the presence of a hydrosilylation catalyst, and specific examples thereof include compounds containing an aliphatic unsaturated bond, organophosphorus compounds, organosulfur compounds, nitrogen-containing compounds, tin compounds, and organic peroxides. Any of these may be used alone, or two or more of these may be used in combination.
- the compounds containing an aliphatic unsaturated bond include propargyl alcohols such as 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol; ene-yne compounds; and maleic anhydride and maleates such as dimethyl maleate.
- organophosphorus compounds include triorganophosphines, diorganophosphines, organophosphones, and triorganophosphites.
- organosulfur compounds include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, and benzothiazole disulfide.
- nitrogen-containing compounds include N,N,N',N'-tetramethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethyl-1,3-propanediamine, N,N,N',N'-tetraethylethylenediamine, N,N-dibutyl-1,4-butanediamine, and 2,2'-bipyridine.
- tin compounds include stannous halide dihydrates and stannous carboxylates.
- organic peroxides include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.
- dimethyl maleate, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol may be mentioned as particularly preferred cure retardants.
- the amount of the cure retardant is not particularly limited, and it preferably ranges from 10 -1 to 10 3 mol, more preferably from 1 to 300 mol, and still more preferably from 1 to 100 mol, per mol of the hydrosilylation catalyst. Any of these cure retardants may be used alone, or two or more of these may be used in combination.
- the polyhedral polysiloxane composition of the present invention can be prepared by mixing the components (A) and (B), and optionally other components such as the above-described hydrosilylation catalyst and cure retardant.
- the polyhedral polysiloxane composition of the present invention can be prepared and handled as a liquid resin composition.
- the liquid resin composition can be injected into or applied to a mold, package, substrate, or the like and then cured to easily provide a molded product suited for the intended use.
- the polyhedral polysiloxane composition of the present invention preferably has a viscosity at 23°C of not less than 1 Pa ⁇ s. This is because the composition exhibits better handleability when used to encapsulate an optical semiconductor device or the like.
- the temperature is preferably selected from 30 to 400°C, and more preferably 50 to 250°C. At too high curing temperatures, cured products with poor appearance tend to be obtained, whereas at too low curing temperatures, the curing may not proceed to a sufficient extent.
- the composition may be cured using a two-step or multi-step temperature profile. More specifically, for example, the curing temperature may preferably be stepwise raised, for example, to 70°C, then to 120°C, and then to 150°C because satisfactory cured products can be obtained.
- the curing period can be appropriately determined according to the curing temperature, the amount of the hydrosilylation catalyst used, and the amount of reactive groups, as well as the combination of other components in the polyhedral polysiloxane composition.
- Cured products obtained by curing the polyhedral polysiloxane composition of the present invention are another aspect of the present invention.
- the polyhedral polysiloxane composition of the present invention may optionally contain an adhesion promoter.
- the adhesion promoter is a component used, for example, to enhance adhesion between the polyhedral polysiloxane composition of the present invention and a substrate.
- the adhesion promoter there is no limitation in selecting the adhesion promoter as long as it exerts such an effect, and preferred examples thereof include silane coupling agents.
- the silane coupling agents are not particularly limited as long as they are compounds each of which has at least one functional group reactive with an organic group, and at least one hydrolyzable silyl group per molecule.
- the functional group reactive with an organic group is preferably at least one functional group selected from the group consisting of epoxy, methacrylic, acrylic, isocyanate, isocyanurate, vinyl, and carbamate groups, in terms of the handleability. In terms of the curability and adhesion, epoxy, methacrylic, and acrylic groups are particularly preferred.
- the hydrolyzable silyl group is preferably an alkoxysilyl group in terms of the handleability, and in particular, methoxysilyl and ethoxysilyl groups are preferred in terms of the reactivity.
- silane coupling agents include alkoxysilanes containing an epoxy functional group, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane; and alkoxysilanes containing a methacrylic or acrylic group, such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysi
- the amount of the silane coupling agent is preferably 0.05 to 30 parts by weight, and more preferably 0.1 to 10 parts by weight, for each 100 parts by weight of a mixture of the components (A) and (B). If the amount is small, the effect of improving adhesion may not be obtained. If the amount is large, the physical properties of the cured products may be adversely affected.
- a known adhesion enhancer may also be used in order to enhance the effect of the adhesion promoter.
- the adhesion enhancer include, but are not limited to, epoxy-containing compounds, epoxy resins, boronic acid ester compounds, organoaluminum compounds, and organotitanium compounds.
- the polyhedral polysiloxane composition of the present invention may optionally contain an inorganic filler.
- an inorganic filler can improve the physical properties of molded products to be obtained, in terms of the strength, hardness, elastic modulus, coefficient of thermal expansion, thermal conductivity, heat dissipation, electrical characteristics, light reflectance, flame retardancy, fire resistance, gas-barrier properties, and the like.
- the inorganic filler is not particularly limited as long as it is an inorganic material or a compound that contains an inorganic material, and specific examples thereof include silica-based inorganic fillers (e.g. quartz, fumed silica, precipitated silica, silicic anhydride, molten silica, crystalline silica, ultrafine amorphous silica), alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, glass flakes, alumina fiber, carbon fiber, mica, black lead, carbon black, ferrite, graphite, diatomaceous earth, white clay, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloons, and silver powder. Any of these may be used alone, or two or more of these may be used in combination.
- the inorganic filler may appropriately be surface-treated.
- the surface treatment include, but are not limited to, alkylation treatment, trimethylsilylation treatment, silicone treatment, and treatment with a silane coupling agent.
- Inorganic fillers having various shapes such as crushed, flake, spherical, and rod shapes may be used.
- the average particle size and particle size distribution of the inorganic filler are not particularly limited, and the preferred average particle size ranges from 0.005 to 50 ⁇ m, more preferably from 0.01 to 20 ⁇ m, in terms of the gas-barrier properties.
- the BET specific surface area thereof is not particularly limited either, and it is preferably not less than 70 m 2 /g, more preferably not less than 100 m 2 /g, and particularly preferably not less than 200 m 2 /g, in terms of the gas-barrier properties.
- the amount of the inorganic filler added is not particularly limited, and is preferably 1 to 1000 parts by weight, more preferably 3 to 500 parts by weight, and still more preferably 5 to 300 parts by weight, for each 100 parts by weight of the mixture of the components (A) and (B) .
- a large amount of inorganic filler added may reduce the fluidity of the composition, whereas a small amount of inorganic filler may not provide desired physical properties.
- the order of mixing of the inorganic filler is not particularly limited.
- a preferred order in terms of better storage stability is mixing the inorganic filler with the component (B) followed by mixing with the component (A).
- Another preferred order is mixing the inorganic filler with a mixture of the components (A) and (B) because the reaction components, namely, the components (A) and (B) are well mixed so that stable molded products tend to be obtained.
- the means for mixing the inorganic filler is not particularly limited, and specific examples thereof include stirring apparatus such as two-roll or three-roll mills, planetary stirring and defoaming apparatus, homogenizers, dissolvers, and planetary mixers, and melt-kneaders such as plastomill.
- the inorganic filler may be mixed at ordinary temperature or under heated conditions, and may be mixed at ordinary pressure or under vacuum conditions. If the inorganic filler is mixed at elevated temperatures, the composition may be cured before molding.
- the polyhedral polysiloxane composition of the present invention may optionally contain various additives (e.g. phosphors, colorants, and heat-resistance improving agents), reaction control agents, mold release agents, dispersants for fillers, and the like.
- additives e.g. phosphors, colorants, and heat-resistance improving agents
- reaction control agents e.g. phosphors, colorants, and heat-resistance improving agents
- mold release agents e.g. phosphors, colorants, and heat-resistance improving agents
- dispersants for fillers include diphenylsilanediol, various alkoxysilanes, carbon-functional silanes, and silanol group-containing siloxanes with low molecular weights.
- the polyhedral polysiloxane composition of the present invention may be prepared by homogeneously mixing the above components with a kneading machine such as a roll mill, Banbury mixer, or kneader, or with a planetary stirring and defoaming apparatus, and optionally performing a heating treatment.
- a kneading machine such as a roll mill, Banbury mixer, or kneader
- a planetary stirring and defoaming apparatus optionally performing a heating treatment.
- the polyhedral polysiloxane composition of the present invention may be converted into and used as a molded product.
- the molding method may be any method such as extrusion molding, compression molding, blow molding, calender molding, vacuum molding, foam molding, injection molding, liquid injection molding, and cast molding.
- peripheral materials for liquid crystal display devices such as substrate materials, light guide plates, prism sheets, polarizing plates, retardation films, viewing angle compensation films, adhesives, color filters, and films for LCDs such as polarizer protective films and passivation films.
- PDPs plasma display panels
- encapsulants such as encapsulants, anti-reflection films, optical compensation films, housing materials, protection films for front glass, alternative materials for front glass, adhesives, color filters, and passivation films
- materials for LED devices such as molding materials for LED elements, protection films for front glass, alternative materials for front glass, adhesives, color filters, and passivation films
- materials for plasma address liquid crystal displays such as substrate materials, light guide plates, prism sheets, polarizing plates, retardation films, viewing angle compensation films, adhesives, color filters, polarizer protective films, and passivation films
- materials for organic EL displays such as protection films for front glass, alternative materials for front glass, color filters, adhesives, and passivation films
- materials for field emission displays FEDs
- Examples of the applications in the optical recording field include materials for VDs (video disks), CD/CD-ROMs, CD-R/RWs, DVD-R/DVD-RAMs, MO/MDs, PDs (phase-change disks), and optical cards, such as disk substrate materials, pickup lenses, protective films, encapsulants, and adhesives. More specifically, there may be mentioned materials for optical pickups of next-generation DVDs and the like, such as pickup lenses, collimator lenses, objective lenses, sensor lenses, protective films, encapsulants for elements, encapsulants for sensors, gratings, adhesives, prisms, wave plates, correcting plates, splitters, holograms, and mirrors.
- Examples of the applications in the optical equipment field include materials for still cameras, such as materials for lenses, prism finders, target prisms, finder covers, and light sensors; materials for video cameras, such as taking lenses and finders; materials for projection televisions, such as projector lenses, protective films, encapsulants, and adhesives; and materials for optical sensing equipment, such as materials for lenses, encapsulants, adhesives, and films.
- peripheral materials for optical switches in optical communication systems such as fiber materials, lenses, waveguides, and encapsulants and adhesives for elements
- peripheral materials for optical connectors such as optical fiber materials, ferrules, encapsulants, and adhesives
- materials for passive optical components and optical circuit components such as lenses, waveguides, and encapsulants and adhesives for LED elements
- peripheral materials for opto-electronic integrated circuits (OEICs) such as substrate materials, fiber materials, and encapsulants and adhesives for elements.
- Examples of the applications in the optical fiber field include materials for decoration displays, such as lighting and light guides; sensors, indications, signs and the like for industrial use; and optical fibers for communications infrastructures and for home networking of digital devices.
- peripheral materials for semiconductor integrated circuits include interlayer insulators, passivation films, and resist materials for microlithography for LSI and ultra LSI materials.
- Examples of the applications in the automotive and transport fields include materials for automobiles, such as lamp reflectors, bearing retainers, gear parts, corrosion-resistant coatings, switch parts, headlamps, inner parts of the engine, electrical parts, various interior and exterior parts, driving engines, brake-oil tanks, rust-proof steel plates for automobiles, interior panels, interior materials, protecting/binding wire harnesses, fuel hoses, automotive lamps, and glass substitutes.
- materials for automobiles such as lamp reflectors, bearing retainers, gear parts, corrosion-resistant coatings, switch parts, headlamps, inner parts of the engine, electrical parts, various interior and exterior parts, driving engines, brake-oil tanks, rust-proof steel plates for automobiles, interior panels, interior materials, protecting/binding wire harnesses, fuel hoses, automotive lamps, and glass substitutes.
- Other examples include multilayer glasses for railway vehicles.
- Further examples include materials for aircrafts, such as toughening agents for structural materials, peripheral members of the engine, protecting/binding wire harnesses, and corrosion-resistant coatings.
- Examples of the applications in the architecture field include interior/processing materials, lamp covers, sheets, glass interlayer films, glass substitutes, and peripheral materials for solar cells.
- Examples in the agricultural field include cover films for greenhouses.
- next generation optical/electronic functional organic materials examples include next-generation DVDs; peripheral materials for organic EL elements; organic photorefractive elements; light-light conversion devices such as optical amplifiers and optical computing elements; and peripheral materials for organic solar cells, such as substrate materials, fiber materials, and encapsulants and adhesives for elements.
- Optical semiconductor devices including the polyhedral polysiloxane composition of the present invention as an encapsulant are also another aspect of the present invention.
- SiH value the amount mined by mixing a tested compound with dibromoethane, dissolving the mixture in deuterated chloroform, performing NMR analysis on the solution by 300 MHz NMR (available from Varian Technologies Japan, Ltd.), and calculating the SiH value using the following equation (1):
- SiH value (mol/kg) [integrated peak value of SiH group of compound]/[integrated peak value of methyl group of dibromoethane] ⁇ 4 ⁇ [weight of dibromoethane in mixture]/[molecular weight of dibromoethane]/[weight of compound in mixture] (1).
- a polyhedral polysiloxane composition was charged into a mold and heat-cured in a convection oven for two hours at 80°C followed by one hour at 100°C and then five hours at 150°C. In this manner, a 2 mm-thick sample was prepared.
- a metaling weather meter (model: M6T, available from Suga Test Instruments Co., Ltd.) was used. Each sample obtained in the manner described above was irradiated at a black panel temperature of 120°C and an irradiance of 0.53 kW/m 2 until the total irradiance reached 50 MJ/m 2 , and then visually observed.
- a single piece of single-crystal silicon chip with a size of 0.4 mm ⁇ 0.4 mm ⁇ 0.2 mm was bonded to an LED package (product name: TOP LED 1-IN-1, available from Enomoto Co., Ltd.) with an epoxy adhesive (product name: Loctite 348, available from Henkel Japan Ltd.), and the resulting LED package was heated for 30 minutes in a convection oven set at 150°C so that the chip was fixed on the LED package.
- a polyhedral polysiloxane composition was then injected into the LED package, and then heat-cured in a convection oven for two hours at 80°C followed by one hour at 100°C and then five hours at 150°C. In this manner, a sample was prepared.
- the moisture permeability of a cured product to be obtained is used as a measure of the gas-barrier properties of the cured product.
- a lower moisture permeability corresponds to a higher level of gas-barrier properties.
- a polyhedral polysiloxane composition was charged into a mold and heat-cured in a convection oven for two hours at 80°C followed by one hour at 100°C and then five hours at 150°C. In this manner, a sample (5 cm square, 2 mm thick) was prepared. This sample was aged for 24 hours at room temperature (25°C) at a humidity of 55%RH.
- Moisture permeability g / m 2 / day weight of entire test sample after moisture permeability test g ⁇ weight of entire test sample before moisture permeability test g ⁇ 1000 / 9
- a polyhedral polysiloxane composition was injected into an LED package (product name: TOP LED 1-IN-1, available from Enomoto Co., Ltd.) and heat-cured in a convection oven for two hours at 80°C followed by one hour at 100°C and then five hours at 150°C. In this manner, a sample was prepared. This sample was placed in a flow gas corrosion tester (available from Fact K Co., Ltd., KG130S) and subjected to a hydrogen sulfide exposure test for 96 hours under the conditions of 40°C, 80%RH, and 3 ppm of hydrogen sulfide.
- a flow gas corrosion tester available from Fact K Co., Ltd., KG130S
- Samples were evaluated as "good” when no color change was observed on a reflector of the package after the test, as “intermediate” when a slight color change was observed, and as “bad” when color changes were observed.
- a polyhedral polysiloxane composition was added 0.05 g of a phosphor (available from Intematix, Y3957), and the mixture was stirred well and then left standing still. During this time the mixture was observed every hour.
- a phosphor available from Intematix, Y3957
- Tetraethoxysilane (1083 g) was added to a 48% aqueous solution of choline (aqueous solution of trimethyl (2-hydroxyethyl) ammonium hydroxide, 1262 g), and the mixture was vigorously stirred at room temperature for two hours. When the reaction system generated heat and turned into a homogeneous solution, the stirring was slowed down and then the solution was left to react for 12 hours. Then, to a solid formed in the reaction system, methanol (1000 mL) was added to give a homogeneous solution.
- choline aqueous solution of trimethyl (2-hydroxyethyl) ammonium hydroxide
- a 5.00 g portion of the tris(vinyldimethylsiloxy)-pentakis(trimethylsiloxy)octasilsesquioxane (an alkenyl group-containing polyhedral polysiloxane compound) prepared in Production Example 1 was dissolved in toluene (10.0 g), and combined with a xylene solution (0.48 ⁇ L) of a platinum-vinylsiloxane complex (platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X).
- platinum-vinylsiloxane complex platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X.
- vinyldiphenylmethylsilane (3.37 g, an amount such that the number of alkenyl groups is 0.29 per hydrosilyl group of the 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane used) was dissolved in toluene (3.37 g), and combined with a xylene solution (0.56 ⁇ L) of a platinum-vinylsiloxane complex (platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X) .
- platinum-vinylsiloxane complex platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X
- a 5.00 g portion of the tris(vinyldimethylsiloxy)-pentakis(trimethylsiloxy)octasilsesquioxane (an alkenyl group-containing polyhedral polysiloxane compound) prepared in Production Example 1 was dissolved in toluene (10.0 g), and combined with a xylene solution (0.48 ⁇ L) of a platinum-vinylsiloxane complex (platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X).
- platinum-vinylsiloxane complex platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X.
- the resulting solution was slowly added dropwise to a solution of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (3.09 g, an amount such that the number of hydrosilyl groups is 4.0 per alkenyl group of the tris(vinyldimethylsiloxy)-pentakis(trimethylsiloxy)octasilsesquioxane used) in toluene (3.09 g), and left to react at 105°C for two hours.
- the reaction solution was sampled and analyzed by NMR to confirm that no peak associated with the alkenyl group was present.
- vinyldiphenylmethylsilane (3.37 g, an amount such that the number of alkenyl groups is 0.29 per hydrosilyl group of the 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane used) was dissolved in toluene (3.37 g), and combined with a xylene solution (0.56 ⁇ L) of a platinum-vinylsiloxane complex (platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X) .
- platinum-vinylsiloxane complex platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X
- Vinyldiphenylmethylsilane (3.37 g, an amount such that the number of alkenyl groups is 0.29 per hydrosilyl group of the 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane used) was dissolved in toluene (3.37 g), and combined with a xylene solution (0.56 ⁇ L) of a platinum-vinylsiloxane complex (platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X).
- platinum-vinylsiloxane complex platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X.
- the resulting solution was slowly added dropwise to a solution of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (3.09 g, an amount such that the number of hydrosilyl groups is 4.0 per alkenyl group of the tris(vinyldimethylsiloxy)-pentakis(trimethylsiloxy)octasilsesquioxane used) in toluene (3.09 g), and left to react at 105°C for one hour.
- the reaction solution was sampled and analyzed by NMR to confirm that no peak associated with the alkenyl group was present.
- a 5.00 g portion of the tris(vinyldimethylsiloxy)-pentakis(trimethylsiloxy)octasilsesquioxane (an alkenyl group-containing polyhedral polysiloxane compound) prepared in Production Example 1 was dissolved in toluene (16.73 g), and combined with vinyldiphenylmethylsilane (3.37 g, an amount such that the number of alkenyl groups is 0.29 per hydrosilyl group of the 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane used) and a xylene solution (1.04 ⁇ L) of a platinum-vinylsiloxane complex (platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X).
- platinum-vinylsiloxane complex platinum-vinyl
- a 5.00 g portion of the tris(vinyldimethylsiloxy)-pentakis(trimethylsiloxy)octasilsesquioxane (an alkenyl group-containing polyhedral polysiloxane compound) prepared in Production Example 1 was dissolved in toluene (10.0 g), and combined with a xylene solution (0.47 ⁇ L) of a platinum-vinylsiloxane complex (platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X).
- platinum-vinylsiloxane complex platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X.
- a 5.00 g portion of the tris(vinyldimethylsiloxy)-pentakis(trimethylsiloxy)octasilsesquioxane (an alkenyl group-containing polyhedral polysiloxane compound) prepared in Production Example 1 was dissolved in toluene (10.0 g), and combined with a xylene solution (0.47 ⁇ L) of a platinum-vinylsiloxane complex (platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X).
- platinum-vinylsiloxane complex platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X.
- Example 1 Example 2
- Example 3 Example 4 Comparative Example 1 Comparative Example 2
- Viscosity (Pa ⁇ s) 2.4 2.2 2.1 2.1 0.04 0.05 Heat resistance test Good Good Good Good Good Good Good Good Light resistance test Good Good Good Good Good Good Thermal shock test Good Good Good Good Good Bad Bad
- Moisture permeability test 10.6 11.8 11.1 11.4 11.2 16.2
- Sulfuration resistance test Good Good Good Good Good Good Intermediate Phosphor settling test Good Good Good Good Good Bad Bad Bad
- the polyhedral polysiloxane compositions of the present invention which contained the components (A) and (B1) had high heat resistance and high light resistance, were excellent in thermal shock resistance and gas-barrier properties, and had a viscosity that ensures good handleability for encapsulating optical semiconductor devices.
- a 10.00 g portion of the tris(vinyldimethylsiloxy)-pentakis(trimethylsiloxy)octasilsesquioxane (an alkenyl group-containing polyhedral polysiloxane compound) prepared in Production Example 1 was dissolved in toluene (20.0 g), and combined with a xylene solution (0.94 ⁇ L) of a platinum-vinylsiloxane complex (platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X).
- platinum-vinylsiloxane complex platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X.
- vinyldiphenylmethylsilane (5.78 g, an amount such that the number of alkenyl groups is 0.25 per hydrosilyl group of the 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane used) was dissolved in toluene (5.78 g), and this solution was slowly added dropwise to the former solution.
- ethynylcyclohexanol (1.79 ⁇ l) and dimethyl maleate (0.41 ⁇ l) were added and toluene was evaporated to give 20.08 g of a liquid modified polyhedral polysiloxane (SiH value: 1.51 mol/kg).
- a 10.00 g portion of the tris(vinyldimethylsiloxy)-pentakis(trimethylsiloxy)octasilsesquioxane (an alkenyl group-containing polyhedral polysiloxane compound) prepared in Production Example 1 was dissolved in toluene (33.48 g), and combined with vinyldiphenylmethylsilane (6.74 g, an amount such that the number of alkenyl groups is 0.28 per hydrosilyl group of the 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane used) and a xylene solution (0.94 ⁇ L) of a platinum-vinylsiloxane complex (platinum-vinylsiloxane complex containing 3 wt% of platinum, available from Umicore Precious Metals Japan Co., Ltd., Pt-VTSC-3X).
- platinum-vinylsiloxane complex platinum-viny
- a 10 . 00 g portion of the modified polyhedral polysiloxane prepared in Production Example 2 was combined with diallyl methyl isocyanurate (1.13 g) and 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (1.12 g), and the mixture was stirred to prepare a polyhedral polysiloxane composition.
- the composition thus obtained was evaluated by the above methods. Table 2 shows the results.
- Example 5 Example 6
- Example 7 Viscosity (Pa ⁇ s) 4.8 5.9 4.4 4.7 Heat resistance test Good Good Good Good Good Light resistance test Good Good Good Good Thermal shock test Good Good Good Good Good Moisture permeability test 5.1 5.3 7.2 6.1 Sulfuration resistance test Good Good Good Good Phosphor settling test Good Good Good Good Good
- the polyhedral polysiloxane compositions of the present invention which contained the components (A) together with the component (B2) or the components (B2) and (B1) had high heat resistance and high light resistance, and were excellent in thermal shock resistance and gas-barrier properties.
- the polyhedral polysiloxane compositions of the present invention can be suitably used as encapsulants of various types . Such encapsulants can be used to fabricate optical devices, optical semiconductor devices, and the like.
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Claims (21)
- Polysiloxane polyèdre modifié, qui est un produit d'hydrosilylation d'un composé de polysiloxane polyèdre contenant un groupe alcényle (a) et d'un composé contenant un groupe hydrosilyle (b), et a une structure dérivée d'un composé de silicium organique (a') ayant un groupe alcényle par molécule et ayant au moins un groupe aryle,
dans lequel le composé de polysiloxane polyèdre contenant un groupe alcényle (a) est un composé de polysiloxane polyèdre contenant un groupe alcényle comprenant un motif siloxane représenté par la formule :
[Ar1 2SiO-SiO3/2]a[R2 3SiO-SiO3/2]b
où a+b est un nombre entier de 6 à 24, à condition que a soit un nombre entier de 1 ou plus et que b soit un nombre entier de 0 ou 1 ou plus ; A est alcényle ; R1 est alkyle ou aryle ; et R2 est hydrogène, alkyle, aryle ou un groupe lié à un autre polysiloxane polyèdre, et
dans lequel le composé contenant un groupe hydrosilyle (b) est au moins un parmi un siloxane cyclique contenant des groupes hydrosilyle et un siloxane linéaire contenant des groupes hydrosilyle. - Polysiloxane polyèdre modifié selon la revendication 1,
dans lequel le polysiloxane polyèdre modifié est sous forme liquide à 20 °C. - Polysiloxane polyèdre modifié selon la revendication 2,
dans lequel le groupe aryle est directement lié à un atome de silicium. - Polysiloxane polyèdre modifié selon l'une quelconque des revendications 1 à 3,
dans lequel le composé contenant des groupes hydrosilyle (b) est un siloxane cyclique contenant des groupes hydrosilyle. - Polysiloxane polyèdre modifié selon la revendication 4,
dans lequel le composé contenant des groupes hydrosilyle (b) est un 1,3,5,7-tétrahydrogéno-1,3,5,7-tétraméthylcyclotétrasiloxane. - Polysiloxane polyèdre modifié, comprenant un motif siloxane représenté par la formule :
[XR3 2SiO-SiO3/2]a[R4 3SiO-SiO3/2]b
où a+b est un nombre entier de 6 à 24, à condition que a soit un nombre entier de 1 ou plus et que b soit un nombre entier de 0 ou 1 ou plus ; R3 est alkyle ou aryle ; R4 est alcényle, hydrogène, alkyle, aryle ou un groupe lié à un autre polysiloxane polyèdre ; et X a une structure représentée par la formule (1) ou (2) suivante, et dans le cas où de multiples X sont présents, les structures de la formule (1) ou (2) peuvent être différentes l'une de l'autre et les structures des formules (1) et (2) peuvent coexister :
-[CH2]1-R5 (3)
où 1 est un nombre entier de 2 ou plus, et R5 est un groupe contenant un composé de silicium organique et ayant au moins un groupe aryle ; et R est alkyle ou aryle. - Polysiloxane polyèdre modifié selon la revendication 6,
dans lequel le groupe aryle est directement lié à un atome de silicium. - Polysiloxane polyèdre modifié selon l'une quelconque des revendications 1 à 7,
dans lequel le polysiloxane polyèdre modifié a au moins trois groupes hydrosilyle en moyenne par molécule. - Composition de polysiloxane polyèdre, comprenant le polysiloxane polyèdre modifié (A) selon l'une quelconque des revendications 1 à 8.
- Composition de polysiloxane polyèdre selon la revendication 9, comprenant en outre un composé (B) ayant au moins deux groupes alcényle par molécule.
- Composition de polysiloxane polyèdre selon la revendication 10,
dans laquelle le composé (B) est un polysiloxane (B1) ayant au moins deux groupes alcényle par molécule. - Composition de polysiloxane polyèdre selon la revendication 11,
dans laquelle le polysiloxane (B1) ayant au moins deux groupes alcényle par molécule a au moins un groupe aryle. - Composition de polysiloxane polyèdre selon la revendication 10,
dans laquelle le composé (B) est un composé organique (B2) représenté par la formule (4) suivante et ayant au moins deux groupes alcényle par molécule : - Composition de polysiloxane polyèdre selon la revendication 13,
dans laquelle le composé organique (B2) a un poids moléculaire moyen en nombre inférieur à 900. - Composition de polysiloxane polyèdre selon la revendication 13 ou 14,
dans laquelle le composé organique (B2) est au moins un composé choisi dans le groupe constitué par l'isocyanurate de triallyle, l'isocyanurate de diallyle, l'isocyanurate de diallyl monométhyle, et l'isocyanurate de diallyl monoglycidyle. - Composition de polysiloxane polyèdre selon la revendication 13 ou 14,
dans laquelle le composé organique (B2) est un isocyanurate de diallyl monométhyle. - Composition de polysiloxane polyèdre selon l'une quelconque des revendications 9 à 16,
dans laquelle la composition de polysiloxane polyèdre a une viscosité à 23 °C non inférieure à 1 Pa·s. - Composition de polysiloxane polyèdre selon l'une quelconque des revendications 9 à 17, comprenant un catalyseur d'hydrosilylation.
- Composition de polysiloxane polyèdre selon l'une quelconque des revendications 9 à 18, comprenant un retardateur de durcissement.
- Produit durci, obtenu par durcissement de la composition de polysiloxane polyèdre selon l'une quelconque des revendications 9 à 19.
- Dispositif optique semi-conducteur, comprenant le produit durci selon la revendication 20.
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PCT/JP2011/070854 WO2012039322A1 (fr) | 2010-09-22 | 2011-09-13 | Polysiloxane modifié à structure polyédrique, composition à base de polysiloxane à structure polyédrique, produit durci, et dispositif semi-conducteur optique |
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US (1) | US9698320B2 (fr) |
EP (1) | EP2620441B1 (fr) |
JP (1) | JP5784618B2 (fr) |
KR (1) | KR101886173B1 (fr) |
CN (1) | CN103119048B (fr) |
TW (2) | TWI526477B (fr) |
WO (1) | WO2012039322A1 (fr) |
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KR101886173B1 (ko) | 2018-08-08 |
TW201221556A (en) | 2012-06-01 |
US9698320B2 (en) | 2017-07-04 |
CN103119048B (zh) | 2016-06-01 |
TWI526477B (zh) | 2016-03-21 |
EP2620441A1 (fr) | 2013-07-31 |
JPWO2012039322A1 (ja) | 2014-02-03 |
TW201612217A (en) | 2016-04-01 |
US20130237663A1 (en) | 2013-09-12 |
JP5784618B2 (ja) | 2015-09-24 |
WO2012039322A1 (fr) | 2012-03-29 |
KR20130097197A (ko) | 2013-09-02 |
EP2620441A4 (fr) | 2014-10-15 |
TWI567114B (zh) | 2017-01-21 |
CN103119048A (zh) | 2013-05-22 |
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